ES2398700T5 - Paper coating procedure - Google Patents

Description

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DESCRIPTION

Paper coating procedure

The present invention relates to a process for coating paper by extrusion processes, characterized in that a biodegradable, aliphatic-aromatic polyester is used as the coating agent, which contains:

i) 40 to 70 mol%, based on the components ia ii, of one or more derivatives of dicarboxylic acid or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid and acid brazilian;

ii) 60 to 30 mol%, based on components i to ii, of a terephthalic acid derivative;

iii) 98 to 102 mol%, based on components i to ii, of an alkylene diol with 2 to 8 carbon atoms or oxyalkylene diol with 2 to 6 carbon atoms;

iv) 0.01 to 2% by weight, based on the total weight of components ia iii, of a chain extender and / or crosslinking agent selected from the group consisting of: a di- or polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, carboxylic acid anhydride and / or at least trifunctional alcohol, or at least trifunctional carboxylic acid;

v) 0.00 to 50% by weight, based on the total weight of components ia iv, of an organic load selected from the group consisting of: native or plasticized starch, natural fibers, wood dust, and / or an inorganic filler selected from the group consisting of: crete, precipitated calcium carbonate, graphite, plaster, conductive soot, iron oxide, calcium chloride, dolomite, kaolin, silicon dioxide (quartz), sodium carbonate, titanium dioxide , silicate, volastonite, mica, montmorillonite, talc, glass fibers and mineral fibers, and

vi) 0.00 to 2% by weight, based on the total weight of components ia iv, of at least one stabilizer, nucleating agent, sliding and separating agent, surfactant, wax, antistatic, antifogging agent, dye, pigment , UV filter, UV stabilizer or other synthetic material additive;

and with a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg of weight) of 5 to 25 cm3 / 10 cm.

Moreover, the invention relates to processes for coating paper by extrusion processes, characterized in that a polymer mixture containing:

- 5 to 95% by weight of a biodegradable, aliphatic-aromatic polyester according to claim 1,

- 95 to 5% by weight of one or more polymers selected from the group consisting of: polylactic acid, polycaprolactone, polyhydroxyalkanoate, chitosan, gluten and / or one or more aliphatic / aromatic polyesters, such as polybutylene succinate, succinate- polybutylene adipate or polybutylene succinate-sebacate, polybutylene terephthalate-co-adipate,

Y

- 0 to 2% by weight of a compatibility rectifier.

In WO-A 92/09654, WO-A 96/15173, WO-A 2006/097353 to 56 are described, by way of example, terephthalate succinates, adipates, sebacate, -azelainatos and -bibutylates of polybutylene, and WO 2006/074815 describes mixtures of these aliphatic-aromatic polyesters with other biodegradable polymers, such as polylactic acid or polyhydroxyalkanoates. The possibility of coating paper with these polymers or these polymer blends is not explicitly stated in these documents.

In attempts to coat paper with known polyesters and polyester blends, relatively thick layers could be obtained relatively slowly.

Accordingly, the objective of the present invention was to make available polyesters, or mixtures of biodegradable polyesters, which were suitable for paper coating.

Surprisingly, the paper coating procedures mentioned at the beginning were now found, which are characterized in that a polyester with a melt volume index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg weight) of 5 to 25 cm3 / 10 min and / or mixtures of polymers containing such polyesters.

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Especially suitable are polyesters with a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg weight) of 5 to 12 cm3 / 10 min.

If mixtures of polyester polymers with other biodegradable polymers are used, such as polylactic acid in particular, it has been found advantageous that these polymers also have high fluidity.

As an example, polylactic acid with a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg weight) of 4 to 100 cm3 / 10 min, and especially preferably, has been successful. from 9 to 70 cm3 / 10 min as a mixing component.

As already mentioned, mixtures of polymers consisting of a fluid polyester and a fluid mixing component, such as polylactic acid in particular, are especially suitable for coating paper. For the mixture of polymers obtained, a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg of weight) of 4 to 70 cm 3/10 min, and especially preferably 10 to 30, results cm3 / 10 min. Mixtures of fluid polyesters with the mixtures of fluid polymers mentioned above are also suitable for coating paper.

Partially aromatic polyesters based on aliphatic diols and / or aliphatic / aromatic dicarboxylic acids derived from polyester are also understood as polyether esters, polyesteramides or polyethersteramides. To the appropriate partially aromatic polyesters belong linear non-prolonged chain polyesters (WO 92/09654). In particular, suitable mixture components are aliphatic / aromatic polyesters of butanediol, terephthalic acid and aliphatic dicarboxylic acids with 6 to 18 carbon atoms, such as adipic acid, subic acid, azelaic acid, sebacic acid and brazilic acid (by way of example as are described in WO 2006/097353 to 56). Prolonged and / or partially aromatic branched chain polyesters are preferred. The latter are known from the documents cited at the beginning WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, to which reference is expressly made. Similarly mixtures of different partially aromatic polyesters come into consideration.

As mentioned at the beginning, biodegradable, aliphatic-aromatic polyesters containing:

i) 40 to 70 mol%, based on the components ia ii, of one or more derivatives of dicarboxylic acid or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid and acid brazilian;

ii) 60 to 30 mol%, based on components i to ii, of a terephthalic acid derivative;

iii) 98 to 102 mol%, based on components i to ii, of an alkylene diol with 2 to 8 carbon atoms or oxyalkylene diol with 2 to 6 carbon atoms;

iv) 0.01 to 2% by weight, based on the total weight of components ia iii, of a chain extender and / or crosslinking agent selected from the group consisting of: a di- or polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, carboxylic acid anhydride and / or at least trifunctional alcohol, or at least trifunctional carboxylic acid;

v) 0.00 to 50% by weight, based on the total weight of components ia iv, of an organic load selected from the group consisting of: native or plasticized starch, natural fibers, wood dust, and / or an inorganic filler selected from the group consisting of: crete, precipitated calcium carbonate, graphite, plaster, conductive soot, iron oxide, calcium chloride, dolomite, kaolin, silicon dioxide (quartz), sodium carbonate, titanium dioxide , silicate, volastonite, mica, montmorillonite, talc, glass fibers and mineral fibers, and

vi) 0.00 to 2% by weight, based on the total weight of components ia iv, of at least one stabilizer, nucleating agent, sliding and separating agent, surfactant, wax, antistatic, antifogging agent, dye, pigment , UV filter, UV stabilizer or other synthetic material additive;

and with a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg of weight) of 5 to 25 cm3 / 10 cm.

The aliphatic-aromatic polyesters used preferably contain:

i) 52 to 65%, and in particular 58% in moles, based on the components ia ii, of one or more derivatives of dicarboxylic acid or dicarboxylic acids selected from the group consisting of: succinic acid, azelaic acid, Brazilian acid, and preferably adipic acid, particularly preferably sebacic acid;

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ii) 48 to 35, and especially 42 mol%, based on components i to ii, of a terephthalic acid derivative;

iii) 98 to 102 mol%, based on components i to ii, of 1,4-butanediol, and;

iv) 0.01 to 2% by weight, based on the total weight of components ia iii, of a chain extender and / or crosslinking agent selected from the group consisting of: a di- or polyfunctional isocyanate, isocyanurate, oxazoline, carboxylic acid anhydride, such as maleic acid anhydride, epoxide (especially an epoxy-containing poly (meth) acrylate) and / or at least trifunctional alcohol, or at least trifunctional carboxylic acid.

Especially suitable for coating paper are aliphatic-aromatic polyesters with a high fraction of aliphatic dicarboxylic acid from 52 to 65, and especially preferably from 52 to 58 mol%. Thinner layers can be made with a higher fraction of aliphatic dicarboxylic acid in the aliphatic-aromatic polyesters. The sheets constituted by these polyesters show a lower tendency to melt resonance in coating installations.

As aliphatic dicarboxylic acids, adipic acid is preferably suitable, and especially preferably sebacic acid. Polyesters containing sebacic acid have the advantage of being available also as a regenerative raw material, and can be extended to give thinner layers. The sheets constituted by these polyesters also show a lower tendency to melt resonance in coating installations.

The synthesis of the described polyesters is carried out according to the procedures described in WO-A 92/09654, WO-A 96/15173, or preferably in PCT / EP2009 / 054114 and PCT / EP2009 / 054116, preferably in a reaction cascade Two stage First, the dicarboxylic acid derivatives are reacted together with a diol in the presence of a transesterification catalyst to give a prepolyester. In general, this prepolyester has a viscosity index (VZ) of 50 to 100 mL / g, preferably 60 to 80 mL / g. As catalysts, zinc, aluminum, and especially titanium catalysts are commonly used. Titanium catalysts, such as tetra (isopropyl) ortho titanate, and especially tetrabutyl orthotitanate (TBOT), compared to tin, antimony, cobalt and lead catalysts frequently used in the literature, such as tin dioctanate, they have the advantage that the remaining amounts of catalyst left in the product, or the successive product of the catalyst, have lower toxicity. This circumstance is especially important in the case of biodegradable polyesters, since they can reach the environment directly through composting.

With both of the above-mentioned procedures, the desired MVR range can be adjusted simply by selecting procedure parameters, such as residence time, reaction temperature and amount of head extraction in the tower reactor.

MVR adjustments to higher values can be achieved by adding component iv) in the indicated concentration range, or by a compatibility rectifier in the case of polymer blends.

The polyesters according to the invention are then obtained in a second step according to the procedures described in WO 96/15173 and EP-A 488 617. The prepolyester is reacted with vib chain extension agents), by way of example with diisocyanates or with epoxy-containing polymethacrylates in a chain extension reaction to give a polyester with a VZ of 50 to 450 mL / g, preferably 80 to 250 mL / g.

In general, 0.01 to 2% by weight, preferably 0.2 to 1.5% by weight, and especially preferably 0.35 to 1% by weight, based on the total weight, are used of components ia iii, of a crosslinker (iva) and / or chain extension agents (ivb) selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, carboxylic acid anhydride, at least trifunctional alcohol , or a at least trifunctional carboxylic acid. As chain extension agents (ivb), polyfunctional isocyanates, and especially difunctional, isocyanurates, oxazolines, carboxylic acid anhydride or epoxides are considered.

Chain extension agents, as well as alcohols or carboxylic acid derivatives with at least three functional groups can also be understood as crosslinkers. Especially preferred compounds have three to six functional groups. By way of example, cite: tartaric acid, citric acid, malic acid; trimethylolpropane, trimethylolethane; pentaerythrite; polyether triols and glycerin, trimesic acid, trimellitic acid, trimellitic acid anhydride, pyromellitic acid and pyromellitic acid dianhydride. Polyols, such as trimethylolpropane, pentaerythrite, and especially glycerin, are preferred. By means of the components iv, biodegradable polyesters with a structural viscosity can be formed. The rheological behavior of the fusion is improved; Biodegradable polyesters can be made more easily, by way of example they can be better extended by melt solidification, to give sheets. The compounds iv act with shear dilution, that is, the viscosity under load decreases.

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Examples of chain extension agents are explained in more detail below.

In particular, copolymer epoxies containing epoxy groups based on styrene, acrylate and / or methacrylate are understood. The units bearing epoxy groups are preferably glycidyl (meth) acrylates. Copolymers with a glycidyl methacrylate fraction of more than 20 have been shown to be advantageous, especially preferably more than 30, and especially more than 50% by weight copolymer. The equivalent weight of epoxide (EEW) in these polymers is preferably 150 to 3000, and especially preferably 200 to 500 g / equivalent. The average molecular weight (weight average) Mw of the polymers preferably amounts to 2000 to 25000, especially 3000 to 8000. The average molecular weight (numerical average) Mn of the polymers preferably amounts to 400 to 6000, especially 1000 to 4000. The polydispersivity (Q) is generally between 1.5 and 5. Copolymers containing epoxy groups of the type mentioned above are distributed, by way of example, by BASF Resins BV under the Joncryl® ADR brand. Joncryl® ADR 4368 is especially suitable as chain extender.

As a general rule, it is reasonable to add crosslinking compounds (at least trifunctional) at an earlier time of polymerization.

The following compounds are suitable as bifunctional chain extension agents:

IVb aromatic diisocyanate is understood as especially toluylene 2,4-diisocyanate, toluylene 2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'- diisocyanate diphenylmethane, naphthylene 1,5-diisocyanate or xylylene diisocyanate. Among these, 2,2'-, 2,4'- diisocyanate, and 4,4'-diphenylmethane are especially preferred. In general, the latter diisocyanates are used as a mixture. In subordinate amounts, for example up to 5% by weight, based on the total weight, the diisocyanates may also contain uretdione groups, by way of example for the protection of isocyanate groups.

Within the scope of the present invention, an aliphatic diisocyanate is understood as primarily linear or branched alkylene diisocyanates or cycloalkylene diisocyanates with 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example 1,6-hexamethylene diisocyanate , isophorone diisocyanate or methylene bis (4-isocyanoccyclohexane). Especially preferred aliphatic diisocyanates are isophorone diisocyanate, and especially 1,6-hexamethylene diisocyanate.

Preferred isocyanurates include aliphatic isocyanurates, which are derived from alkylene diisocyanates or cycloalkylene diisocyanates with 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example isophorone diisocyanate or methylene bis (4-isocyanoccyclohexane) . In this case, alkylene diisocyanates can be both linear and branched. Especially preferred are isocyanurates based on n-hexamethylene diisocyanate, for example, cyclic trimers, pentamers or higher oligomers of 1,6-hexamethylene diisocyanate.

In general, 2,2'-bisoxazolines are accessible by the Angew procedure. Chem. Int. Ed., Vol. 11 (1972), pages 287-288. Especially preferred bisoxazolines are those in which R 1 means a single bond, a group (CH 2) z-alkylene, with z = 2, 3 or 4, such as methylene, ethan-1,2-diyl, propan-1,3-diyl , propan-1,2-diyl, or a phenylene group. As especially preferred bisoxazolines are 2,2'-bis (2-oxazoline), bis (2- oxazolinyl) methane, 1,2-bis (2-oxazolinyl) ethane, 1,3-bis (2-oxazolinyl) propane or 1 , 4-bis (2-oxazolinyl) butane, especially 1,4-bis (2-oxazolinyl) benzene, 1,2-bis (2-oxazolinyl) benzene or 1,3-bis (2-oxazolinyl) benzene.

The polyesters according to the invention generally have a number average molecular weight (Mn) in the range of 5,000 to 100,000, especially in the range of 10,000 to 75,000 g / mol, preferably in the range of 15,000 to 38,000 g / mol, a weight average molecular weight (Mw) of 30,000 to 300,000, preferably 60,000 to 200,000 g / mol, and an Mw / Mn ratio of 1 to 6, preferably 2 to 4. The viscosity index is between 50 and 450, preferably of 80 to 250 g / mL (measured in o-dichlorobenzene / phenol (weight ratio 50/50). The melting point is in the range of 85 to 150, preferably in the range of 95 to 140 ° C.

The aliphatic dicarboxylic acid i is used in 40 to 70 mol%, preferably 52 to 65 mol%, and particularly preferably 52 to 58 mol%, based on the acid components i and ii. Sebacic acid, azelaic acid and Brazilian acid are accessible from regenerative raw materials, especially from castor oil.

Terephthalic acid ii is used in 60 to 30 mol%, preferably 48 to 35 mol%, based on the acid components i and ii.

Terephthalic acid and aliphatic dicarboxylic acid can be used as free acid, or in the form of derivatives that form esters. As derivatives forming esters, mention should be made of di-alkyl esters having 1 to 6 carbon atoms, such as dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, di-n-butyl-, di- iso-butyl-, di-t-butyl, di-n-pentyl-, di-iso-

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pentyl- or di-n-hexyl ester. Similarly, dicarboxylic acid anhydrides can be used.

In this case, the dicarboxylic acids or their derivatives that form esters can be used separately or as a mixture.

1,4-butanediol is accessible from regenerative raw materials. PCT / EP2008 / 006714 discloses a biotechnological procedure for obtaining 1,4-butanediol starting from different carbohydrates with microorganisms of the Pasteurellaceae class.

As a general rule, at the beginning of the polymerization, the diol (component iii) with respect to acids (components i and ii) is adjusted in a diol ratio to diacids of 1.0 to 2.5: 1, and preferably 1.3 to 2.2: 1. During the polymerization excess amounts of diol are extracted, so that at the end of the polymerization an approximately equimolar ratio is adjusted. Approximately equimolar is a diol / diacid ratio of 0.98 to 1.02: 1.

The said polyesters may have hydroxy and / or carbonyl terminal groups in any proportion. The said partially aromatic polyesters may also be modified in their terminal groups. By way of example, terminal OH groups may be acid modified by reaction with phthalic acid, phthalic acid anhydride, trimellitic acid, trimellitic acid anhydride, pyromellitic acid or pyromellitic acid anhydride. Polyesters with acid indices lower than 1.5 mg KOH / g are preferred.

In a preferred embodiment, 1 to 80% by weight, preferably 5 to 35% by weight, based on the total weight of components ia iv, of an organic filler selected from the group consisting of: native starch is added or plasticized, natural fibers, wood dust, and / or of an inorganic filler selected from the group consisting of: crete, precipitated calcium carbonate, graphite, gypsum, conductive soot, iron oxide, calcium chloride, dolomite, kaolin , silicon dioxide (quartz), sodium carbonate, titanium dioxide, silicate, volastonite, mica, montmorillonite, talc, glass fibers and mineral fibers.

Starch and amylose can be native, that is, not thermoplasticized, or thermoplasticized with plasticizers, such as glycerin or sorbitol (EP-A 539 541, EP-A 575 349, EP 652 910).

Natural fibers are understood as, for example, cellulose fibers, hemp fibers, sisal, kenaf, jute, flax, abaca, coconut fiber or cordenka fibers.

Preferred fibrous fillers include glass fibers, carbon fibers, aramid fibers, potassium titanate fibers and natural fibers, glass fibers such as E glass being especially preferred. These can be used as rovings, or especially as cut glass in the commercial forms These fibers generally have a diameter of 3 to 30 pm, preferably 6 to 20 pm, and especially preferably 8 to 15 pm. The fiber length in the compound generally ranges from 20 pm to 1000 pm, preferably 180 to 500 pm, and especially preferably 200 to 400 pm.

The blends of biodegradable polyesters according to the invention may contain other content substances known to the specialist, but not essential to the invention. By way of example the additives customary in the art of synthetic materials, such as stabilizers; nucleating agents, such as polybutylene terephthalate, N, N'-ethylene-bis-stearylamide, zinc phenyl phosphonate, graphite, talc, crete, precipitated calcium carbonate, kaolin, quartz sand, silicate; sliding agents and separators, such as stearates (especially calcium stearate); plasticizers (plasticizers), such as citrates (especially acetyltributyl citrate), glycerates, such as triacetylglycerin or ethylene glycol derivatives, surfactants, such as polysorbates, palmitates or laurates; waxes, such as beeswax or beeswax esters; antistatic, UV filters; UV stabilizers, anti-fogging agents or dyes. The additives are used in concentrations of 0 to 5% by weight, especially 0.1 to 2% by weight, based on the polyesters according to the invention. The plasticizers can be contained in the polyesters according to the invention in 0.1 to 10% by weight. The use of 0.1 to 1% by weight of nucleating agent is especially preferred.

Obtaining mixtures of biodegradable copolymers according to the invention from the isolated components can be carried out according to known procedures (EP 792 309 and US 5 883 199). By way of example, all mixing components can be mixed and reacted in a process step, in mixing devices known to the specialist, by way of example kneading or extrusion at elevated temperatures, by way of example of 120 ° C at 300 ° C.

Typical copolymer blends contain:

• 5 to 95% by weight, preferably 30 to 90% by weight, especially preferably 50 to 70% by weight of a copolymer according to the invention, and

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• 95 to 5% by weight, preferably 70 to 10% by weight, especially preferably 50 to 30% by weight of one or more polymers selected from the group consisting of: polylactic acid, polycaprolactone, polyhydroxyalkanoate, chitosan and gluten, and one or more polyesters based on aliphatic diols and aliphatic / aromatic dicarboxylic acids, such as polybutylene succinate (PBS), polybutylene succinate-adipate (PBSA), polybutylene succinate-sebacate (PBSSe) , polybutylene terephthalate-co-adipate (PBTA), and

• 0 to 2% by weight of a compatibility rectifier.

For their part, the copolymer mixtures preferably contain 0.05 to 2% by weight of a compatibility rectifier. Preferred compatibility rectifiers are carboxylic acid anhydrides, such as maleic acid anhydride, and especially copolymers containing styrene-based epoxy groups, acrylates and / or methacrylates, described above. The units bearing epoxy groups are preferably glycidyl (meth) acrylates. Copolymers containing epoxy groups of the type mentioned above are distributed, by way of example, by BASF Resins B. V. under the brand name Joncryl® ADR. As an compatibility rectifier, Joncryl® ADR 4368 is particularly suitable as an example.

Mixtures of appropriate polyesters contain

• 20 to 90% by weight, preferably 30% to 50%, particularly preferably 35% to 45% of a copolymer according to claims 1 to 3, and

• 80 to 10% by weight, preferably 70% to 50%, especially preferably 65% to 55% of one or more polymers selected from the group consisting of: polyhydroxyalkanoate, and especially polylactic acid , Y

• 0 to 2% by weight of a poly (meth) acrylate containing epoxide.

Mixtures of polymers can be used as anhydrous mixtures or as compounds.

Biodegradable polyester is suitable, by way of example, polylactic acid. Preferably polylactic acid is used with the following properties profile:

• a volumetric melt index (MVR at 190 ° C and 2.16 kg according to ISO 1133 of 0.5 to 100, preferably 5 to 70, especially preferably 9 to 50 ml / 10 minutes;

• a melting point below 240 ° C;

• a glass transition point (Tg) greater than 55 ° C;

• a water content of less than 1000 ppm;

• a residual monomer content (lactide) less than 0.3%;

• a molecular weight greater than 50 000 Dalton.

Preferred polylactic acids are, by way of example, Natureworks® 6201 D, 6202 D, 6251 D, 3051 D, and especially 3251 D (polylactic acid from Natureworks).

Mixtures of polymers containing an aliphatic-aromatic polyester according to claim 1 and polylactic acid are especially suitable for paper coating. In particular, mixtures of polymers in which the polylactic acid forms the continuous phase have proved suitable in this case. This is often guaranteed in polymer blends containing more than 50% by weight polylactic acid. Compared to pure PLA, these mixtures are distinguished by a reduced strangulation of the fusion heel after leaving the flat nozzle - the so-called neck-in is reduced by at least 10%, preferably 20 to 80%, so Especially preferred at 30 to 60%. In comparison with PBAT poly-butylene adipate-terephthalate, the fusion heel is clearly more stable, and allows a greater extension capacity at <30 g / m2, preferably <20 g / m2, particularly preferably <17 g / m2 The good adhesion to the cellulose substrate (paper, cardboard) is maintained depending on the cooling conditions by high trajectory speeds> 100 m / min.

First, poly-4-hydroxybutyrates and poly-3-hydroxybutyrates are understood as being

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they include copolyesters of the hydroxybutyrates mentioned above with 3-hydroxivalerates or 3-hydroxyhexanoate. Poly-3-hydroxy-butyrates-co-4-hydroxybutyrates are known in particular by Metabolix. They are distributed under the trade name Mirel®. Poly-3-hydroxybutyrates-co-3-hydroxyhexanoates are known by the firm P&G or Kaneka. Poly-3-hydroxybutyrates are distributed, by way of example, by PHB Industrial under the trademark Biocycle® and by Tianan under the name Enmat®.

The polyhydroxyalkanoates generally have a molecular weight Mw of 100,000 to 10,000,000, and preferably 300,000 to 600,000.

Polycaprolactone is marketed by Daicel under the registered trademark Placcel®.

The polyesters and mixtures of polyesters mentioned at the beginning have a marked biodegradable character with simultaneously good film properties.

Within the meaning of the present invention, the "biodegradable" characteristic for a substance or a mixture of substances is met when this substance or the mixture of substances corresponding to DIN EN 13432 has a percentage degree of biological degradation of at least 90%.

In general, the biodegradable character leads to (mixtures of) polyesters decomposing in a suitable and justifiable time interval. The degradation can be carried out by enzymatic, hydrolytic, oxidative and / or electromagnetic radiation action, such as UV radiation, and in most cases, predominantly, through the action of microorganisms, such as bacteria , yeasts, fungi and algae. The biodegradable character can be quantified, by way of example, by mixing polyesters with compost and storing them for a certain time. As an example, according to DIN EN 13432, CO2-free air is allowed to circulate through compost matured during composting, and it is subjected to a defined temperature program. In this case, the biodegradable character is defined by the proportion of net CO2 release of the sample (after deduction of the CO2 release through the compost without sample) with respect to the maximum CO2 release of the sample (calculated at from the carbon content of the sample) as a percentage degree of biological degradation. (Mixtures) of biodegradable polyesters generally show obvious degradation phenomena, such as fungal attack, formation of cracks and holes, already after a few days.

Other methods for determining the biodegradable character are described, by way of example, in ASTM D 5338 and ASTM D 6400-4. The polyesters of the process according to the invention also have very good adherent properties. The extrusion coating, as well as the rolling process, is suitable for obtaining it. A combination of these procedures is also conceivable.

The method according to the invention can be used, for example, for coating paper with monolayers (single layer coating). In this case, the average basic weight is generally 10 to 50, and preferably 15 to 30 g / m2.

The basic weight is determined with the help of die-cut slices, which generally have a diameter of 4.5 inches (114.3 mm). Coated and uncoated slices are weighed. The basic weight in g / m2 can be indicated through the difference in weight and the known surface.

But multilayer paper coatings are also quite common. In general, 2 to 7 layers are used, and preferably 2 to 3 layers in the paper coating. The multilayer coating offers the possibility of optimizing the welding properties, the barrier properties and the adhesion of the coating on cardboard for the insulated layers. In this case, the average basic weight is generally 10 to 60, and preferably 15 to 35 g / m2.

Thus, an outer layer or covering layer should generally be, by way of example, scratch resistant, high temperature stable and low adhesive. The tendency to adhere must be reduced to avoid only an adhesion of the sheet to the cooling cylinder in the process of obtaining.

This is preferably constituted by a mixture of 40 to 60% by weight of an aliphatic-aromatic polyester and 60 to 40% by weight of polylactic acid, and 0 to 10% by weight of a ceramic formulation with a 0 to 5% by weight of wax, 0 to 10% by weight of dispersing agent (for example metal salts of stearic acid, oleic acid, ethylene-bis-stearylamide, acid amide (for example erucic acid amide, oleic acid amide)), and 0 to 5% separating agent.

The intermediate layer is generally more rigid, and can also be called the support layer or barrier layer. In the paper coating with thin films, the central layer can also be completely dispensed with. The intermediate layer preferably contains 50 to 100% by weight of polylactic acid and 0 to 50% by weight of aliphatic-aromatic polyester.

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The inner layer forms the contact layer with the cardboard. As a general rule, it will be softer and will stick conveniently on the cardboard, or the paper. This preferably consists of 50 to 100% of an aliphatic-aromatic polyester and 0 to 50% of polylactic acid.

The coating of three layers of paper is preferred. The coating preferably has the following composition:

i) an outer layer containing a mixture consisting of 40 to 60% by weight of an aliphatic polyester-

aromatic and 60 to 40% by weight of polylactic acid, and 0 to 10% by weight of a ceramic formulation

with wax, auxiliary dispersing agent and separating agent; in general, the outer layer constitutes 20 to 40% of the layer thickness;

ii) a middle layer containing 50 to 100% by weight of polylactic acid and 0 to 50% by weight of aliphatic-aromatic polyester; in general, the middle layer constitutes 20 to 40% of the layer thickness; Y

iii) an inner layer of contact with the cardboard, consisting of 50 to 100% aliphatic-aromatic polyester and 0 to 50% polylactic acid. In general, the inner layer constitutes 20 to 40% of the layer thickness.

Coating of two layers of paper is preferred in the same way. The coating preferably has the following composition:

i) an outer layer containing a mixture consisting of 40 to 60% by weight of an aliphatic polyester-

aromatic and 60 to 40% by weight of polylactic acid, and 0 to 10% by weight of a ceramic formulation

with wax, auxiliary dispersing agent and separating agent; in general, the outer layer constitutes 20 to 50% of the layer thickness;

iii) an inner layer of contact with the cardboard, consisting of 50 to 100% aliphatic-aromatic polyester and 0 to 50% polylactic acid. In this case, the inner layer generally adopts the function of support and / or barrier. In general, the inner layer constitutes 50 to 80% of the layer thickness.

Coextrusion procedures are generally used for multilayer paper coating. Coextrusion coating is preferred.

The extrusion coating was developed to apply thin polymer layers on flexible substrates, such as paper, cardboard, or multilayer sheets with metal layer with high path speeds of 100-600 m / min. The polyesters according to the invention protect the substrate of oil, grease and moisture, and by their aptitude for welding with themselves and paper, cardboard and metal, it makes it possible, for example, to obtain coffee glasses, beverage containers or cartons for frozen products. Polyesters according to the invention can be made in existing extrusion coating facilities for polyethylene (J. Nentwig: Kunststofffolien, Hanser editorial, Münich 2006, page 195; HJ Saechtling; Kunststoff Taschenbuch, Hanser editorial, Münich 2007, page 256; C. Rauwendaal: L Polymer Extrusion, Hanser Verlag, Münich 2004, page 547).

In addition to the high adhesion on paper and cardboard, the polyesters and mixtures of polyesters used in the process according to the invention have a lower tendency to melt resonance in the extrusion coating, compared to known solutions, so that in the Coating process can work with high trajectory speeds, and achieve significant material savings.

The process according to the invention is especially suitable for coating paper for obtaining paper bags for dry food products, such as coffee, tea, powder soups, powdered sauces; for liquids, such as cosmetics, cleaning agents, beverages; of paper bags; of paper coextrusion products for ice cream, sweets (eg chocolate bars and muesly), of paper adhesive tape; of paper cups (cardboard cups), yogurt cups; of menu trays; of rolled cardboard tanks (boats, drums), of moisture-resistant cartons for containers (wine bottles, food products); of trays for coated cardboard fruit; of fast food dishes; of clamping housings; of cartons for beverages and cartons for liquids, such as forging and cleaning agents, cartons for frozen products, containers for ice cream (for example ice cream cups, ice cream cone wrappers); of paper labels; of pots for flowers and plants.

Technical measures of application

The molecular weights Mn and Mw of the partially aromatic polyesters are determined as follows: 15 mg of partially aromatic polyester was dissolved in 10 ml of hexafluorisopropanol (HFIP). Were analyzed

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respectively 125 pl of this solution by means of gel permeation chromatography (GPC). The measurements were carried out at room temperature. For elution HFIP + 0.05% by weight of potassium salt of trifluoroacetic acid was used. The elution rate was 0.5 ml / min. In this case the following combination of columns was used (all columns manufactured by Showa Denko Ltd., Japan); Shodex® HFIP-800P (diameter 8 mm, length 5 cm), Shodex® HFIP-803 (diameter 8 mm, length 30 cm), Shodex® HFIP-803 (diameter 8 mm, length 30 cm). Partially aromatic polyesters were detected by means of an RI detector (differential refractometry). The calibration was carried out with polymethyl methacrylate patterns of narrow distribution, with molecular weights of Mn = 505 to Mn = 2740000. Elution intervals outside this range were determined by extrapolation.

The viscosity indexes were determined according to DIN 53728, part 3, January 3, 1985, capillary viscosimetry. Micro-Ubbelohde, type M-II was used. As a solvent, the mixture was used: phenol / dichlorobenzene in a 50/50 weight ratio.

The volumetric melting index (MVR) was determined according to EN ISO 1133. The test conditions amounted to 190 ° C, 2.16 kg. The melting time was 4 minutes. The MVR indicates the extrusion speed of a molten synthetic molded part through an extrusion tool of a determined length and determined diameter, under the conditions described above: temperature, load and position of the plunger. The volume extruded in a given time in the cylinder of an extrusion plastometer is determined.

The layer thickness was determined from punched slices of 114.3 mm (4.5 inches). The coated and uncoated slice were weighed, and the weight difference was determined, with which the basic weight (weight difference / slice surface) was calculated. The polymer density amounted to 1.25 g / cm3 in the following examples. This could calculate the average layer thicknesses in pm.

The degradation rates of biodegradable polyester blends and mixtures obtained as a comparison were determined as follows:

From the biodegradable polyester mixtures and the mixtures obtained as a comparison, sheets with a thickness of 30 pm were respectively made by pressing at 190 ° C. These sheets were cut respectively into square pieces with edge lengths of 2 x 5 cm. The weight of these laminar pieces was determined in each case and defined as "100% by weight". For a period of four weeks, the laminar pieces were heated at 58 ° C in a drying cabinet, in a synthetic container filled with moistened mulch. At weekly intervals, the remaining weight of the sheet pieces was measured respectively, and the same was converted to% by weight (based on the weight determined at the beginning of the test and defined as "100% by weight").

Test setup

The pilot lining installation (ER-WE-PA) consisted of a main extruder A (Reifenhauser, 80 mm diameter-30 D) and 3 extruders (B, C, D) with 60 mm diameter / 25 D in length . In the case of using Ecoflex F BX 7011 (a polybutylene terephthalate-adipate from BASF SE with an MVR of approximately 2.5 cm3 / 10 min, all MVR values used below are determined according to EN iSo 1133 ( 190 ° C, 2.16 kg of weight)), a yield of approximately 90 kg / h could be achieved in the case of 81 1 / min. The performance of the main extruder (Reifenhauser, 80 mm diameter-30 D) amounted to 190 kg / h with a speed of 77 1 / min. The extruder's performance was varied to achieve as low layer thicknesses as possible.

The coextrusion installation had a nozzle coextrusion tool, which allowed a coextrusion of up to 7 layers with a nozzle width of 1000 mm, and a regulating groove width of 0.5 mm. By means of insertion elements in the fusion channel, several layers could be used together. The installation was equipped with a two-layer adapter insertion element (Cloeren signature, with marginal seal) aAaBBBB, with the main extruder as extruder A, and one as 60 as extruder B. The outer layer A was led to the cardboard with 40% total thickness, the inner layer B with 60% total thickness.

As a cardboard material, a typical coffee cup material was used, which had a surface weight (basic weight) of approximately 200 g / m2. The cardboard material was activated with a flame ionization installation (gas burner) before the incidence of the fusion of synthetic material.

All coatings were extruded onto the cardboard with a mass temperature of 250 ° C and a normal pressure on the 4 bar cooling cylinder. In this case, the trajectory speed was varied between 30 m / min and 200 m / min. Higher speeds led to a fusion resonance in the pilot installation depending on the product.

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Polyesters used Polyester 1

As reference material, Ecoflex F BX 7011 (a polybutylene terephthalate-adipate from BASF SE) was first used with an MVR of 2.5 cm3 / 10 min.

1 / Wax Polyester Blend

Ecoflex Batch SL2, commercially available, based on Ecoflex F BX 7011, containing 5% of a biodegradable wax and 10% of calcium stearate was used to reduce adhesion on the cooling cylinder.

Polyester 2

A polybutylene terephthalate-sebacate with an MVR of 3.3 cm3 / 10 min.

Polyester 2 / Wax Blend

The combination is an anhydrous mixture and contains 85% by weight of polyester, 2.5% of a biodegradable wax, and 10% of calcium stearate.

Polyester 3

A polybutylene terephthalate adipate with an MVR of 8.0 cm3 / 10 min.

Polyester 4

A polybutylene terephthalate-sebacate with an MVR of 6.4 cm3 / 10 min.

1st comparative example

The main extruder A of the pilot installation with polyester 1 was put into operation for the formation of the basic layer on paper, and the secondary extruder B with a mixture consisting of 90% polyester 1 and 10% polyester blend 1 / wax for the formation of the covering layer. The mass temperature was 250 ° C in both cases.

At a maximum path speed of 80 m / min an average layer thickness of 26 pm was reached. The coating could be detached only with fiber breakage in the cardboard matrix. At speeds of trajectory> 80 m / min, the cardboard lining was partially removed without fiber breakage. Fluency instabilities, such as a growth and decrease in yield or a dynamic variation in the melting path width (fusion resonance) were presented only from 120 m / min.

Since polyester 1 is based on fossil raw materials, the fraction of regenerative raw materials in the comparative example was 0%.

2nd comparative example

Under the same conditions as in comparative example 1, polyester 2 was used instead of polyester 1 (basic layer) and polyester 2 / wax mixture instead of polyester 1 / wax mixture (covering layer).

At a maximum path velocity of 80 m / min an average layer thickness of 28.6 pm was reached (-10% reference layer thickness with respect to comparative example 1). The coating could be detached only with fiber breakage in the cardboard matrix. At speeds of trajectory> 80 m / min, the cardboard lining was partially removed without fiber breakage. Fluency instabilities, such as a growth and decrease in yield or a dynamic variation in the melting path width (fusion resonance), occurred only from 150 m / min.

The material savings due to a smaller layer thickness amounted to 10% compared to comparative example 1. The fraction of regenerative raw materials stood at 38%.

3rd Comparative Example

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A compound consisting of 45% polyester 3 and 55% polylactic acid (NatureWorks 3251 D) was used in the secondary extruder B for the covering layer. The main extruder A was driven with polyester 1. The dough temperature was 255 ° C.

At a maximum path speed of 120 m / min an average layer thickness of 19 pm was reached (-41% of reference layer thickness). The coating could be detached only with fiber breakage in the cardboard matrix. Fluency instabilities, such as a growth and decrease in yield or a dynamic variation in the melting path width (melting resonance) were presented at 140 m / min.

The material savings compared to the reference amounted to 41%. The fraction of regenerative raw materials stood at 22%.

4th Example (not according to the invention)

A compound consisting of 24% polyester 4 and 16% polyester 1, and 60% polylactic acid (NatureWorks 3251 D) was used in the main extruder and in the secondary extruders A and B. The mass temperature rose at 258 ° C.

At a maximum path speed of 170 m / min an average layer thickness of 16.5 pm (-48% reference layer thickness) was reached. The coating could be detached only with fiber breakage in the cardboard matrix. Fluency instabilities, such as a growth and decrease in yield or a dynamic variation in the melting path width (fusion resonance) occurred only from 240 m / min. An especially reduced neck-in was observed.

The material savings compared to the reference amounted to 48%. The fraction of regenerative raw materials stood at 69% in this coating.

5th Example - three layer coating (not according to the invention)

The Cloeren power supply block of the installation was transformed so that an AABBBCC structure was produced. In addition to the main extruder, the secondary extruder C was used, which is comparable to the extruder B. The following mixtures were used:

Extruder B (28.5% thick, covering layer): a compound consisting of 24% polyester 4, 16% polyester 3 and 60% polylactic acid (NatureWorks 3251 D).

Extruder A (43% thick, middle layer): a compound consisting of 80% polylactic acid (NatureWorks 3251 D), 20% polyester 2.

Extruder C (28.5% thick, inner layer): a compound consisting of 24% polyester 4, 16% polyester 1 and 60% polylactic acid (NatureWorks 3251 D)

At a maximum path speed of 150 m / min an average layer thickness of 21 pm was reached (-34% of reference layer thickness). The coating could be detached only with fiber breakage in the cardboard matrix. Fluency instabilities, such as a growth and decrease in yield or a dynamic variation in the melting path width (fusion resonance) occurred only from 190 m / min. A reduced neck-in was observed.

With this 3-layer coextrusion, material savings were achieved compared to the 34% reference at a path speed of 150 m / min. The fraction of regenerative raw materials amounted to 77% in this coating.

With the process according to the invention, melt resonance can be substantially avoided. In addition there were no flow instabilities (bands, flow models or dynamically modified performance). Finally, a very good adhesion on paper / cardboard was achieved. This is expressed by a breakage of fibers in the release of paper / cardboard. In particular, thin coatings could be achieved, which led to considerable material savings.

Claims (13)

10 fifteen twenty 25 30 35 1. Procedure for coating paper by printing procedures, characterized in that a biodegradable, aliphatic-aromatic polyester is used as the coating agent, which contains: i) 40 to 70 mol%, based on the components ia ii, of one or more derivatives of dicarboxylic acid or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid and acid brazilian; ii) 60 to 30 mol%, based on components i to ii, of a terephthalic acid derivative; iii) 98 to 102 mol%, based on components i to ii, of an alkylene diol with 2 to 8 carbon atoms or oxyalkylene diol with 2 to 6 carbon atoms; iv) 0.01 to 2% by weight, based on the total weight of components ia iii, of a chain extender and / or crosslinking agent selected from the group consisting of: a di- or polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, carboxylic acid anhydride and / or at least trifunctional alcohol, or at least trifunctional carboxylic acid; v) 0.00 to 50% by weight, based on the total weight of components ia iv, of an organic load selected from the group consisting of: native or plasticized starch, natural fibers, wood dust, and / or an inorganic filler selected from the group consisting of: crete, precipitated calcium carbonate, graphite, plaster, conductive soot, iron oxide, calcium chloride, dolomite, kaolin, silicon dioxide (quartz), sodium carbonate, titanium dioxide , silicate, volastonite, mica, montmorillonite, talc, glass fibers and mineral fibers, and vi) 0.00 to 2% by weight, based on the total weight of components ia iv, of at least one stabilizer, nucleating agent, sliding and separating agent, surfactant, wax, antistatic, antifogging agent, dye, pigment , UV filter, UV stabilizer or other synthetic material additive; and with a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg of weight) of 5 to 25 cm) * 3/10 cm. 2. Procedure for coating paper by extrusion procedures, characterized in that a polymer mixture containing: - 5 to 95% by weight of a biodegradable, aliphatic-aromatic polyester, according to claim 1; Y - 95 to 5% by weight of one or more polymers selected from the group consisting of: polylactic acid, polycaprolactone, polyhydroxyalkanoate, chitosan, gluten, and one or more aliphatic / aromatic polyesters, such as polybutylene succinate, succinate adipate of polybutylene or polybutylene succinate-sebacate, polybutylene terephthalate-co-adipate; Y - 0 to 2% by weight of a compatibility rectifier. 3. Method according to claim 1 or 2, the components i) and ii) of polyester being defined as follows: i) 52 to 65 mol%, based on the components ia ii, of one or more derivatives of dicarboxylic acid or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid and acid brazilian; ii) 48 to 35 mol%, based on components i to ii, of a terephthalic acid derivative. 4. Process according to claim 1 or 2, using component i) of the polyester sebacic acid or mixtures of sebacic acid with the other diacids. 5. Process according to claim 2, containing the polymer mixture - 20 to 90% by weight of a polyester of components i) to vi), 5 10 fifteen twenty 25 30 - 80 to 10% by weight of polylactic acid, and - 0 to 2% by weight of a poly (meth) acrylate containing epoxide. 6. Method according to claim 5, the polylactic acid having a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg weight) of 9 to 70 cm3 / 10 min. 7. Method according to claim 5, the polymer mixture having a volumetric melt index (MVR) according to EN ISO 1133 (190 ° C, 2.16 kg weight) of 10 to 30 cm3 / 10 min. 8. Process according to claim 5, the polylactic acid forming in the polymer mixture the continuous phase. 9. Process according to claims 1 to 5, the polymer mixture containing 0.1 to 1% by weight nucleating agent. 10. Procedure for multilayer paper coating according to claims 1 to 9, by means of the coextrusion process. 11. Method for coating three layers of paper according to claim 10 with i) an outer layer containing a mixture consisting of 40 to 60% by weight of an aliphatic-aromatic polyester and 60 to 40% by weight of polylactic acid, and 0 to 10% by weight of a formulation wax wax, dispersing auxiliary agent and separating agent; ii) if appropriate, a middle layer containing 50 to 100% by weight of polylactic acid and 0 to 50% by weight of aliphatic-aromatic polyester; Y iii) an inner layer of contact with the cardboard, consisting of 50 to 100% aliphatic-aromatic polyester and 0 to 50% polylactic acid. 12. Method for coating two layers of paper according to claim 10 with i) an outer layer containing a mixture consisting of 40 to 60% by weight of an aliphatic-aromatic polyester and 60 to 40% by weight of polylactic acid, and 0 to 10% by weight of a formulation wax wax, dispersing auxiliary agent and separating agent; Y iii) an inner layer of contact with the cardboard, consisting of 50 to 100% aliphatic-aromatic polyester and 0 to 50% polylactic acid. 13. Method for coating paper according to claims 1 to 12 for obtaining paper bags for dry foodstuffs, liquids, paper bags, paper coextrusion products, paper adhesive tape, cardboard cups, yogurt cups , menu trays, rolled cardboard containers, moisture-resistant cartons for external packaging, trays for coated cardboard fruit, fast food plates, holding housings, beverage cartons, liquid cartons, frozen product cartons, packaging for Ice cream, paper labels, flowerpots and plants.